Composition of matter and method of making same



Patented Sept. 12, 1944 UNITED ST COMPOSITION OF or MATTER AND METHODMAKING SAME Melvin De Groote, University City, and Bernhard Kaiser,'Webster Groves, Mo.,

assignors to Petrolite Corporation, Ltd., Wilmington, Del, a

corporation of Delaware No Drawing. Application August 2, 1948,

Serial No. 497,118

' 9 Claims.

This invention relates to a new chemical product or composition ofmatter, our present application being a continuation-in-part of ourcopending application Serial No. 447,151, filed June 15, 1942.

The main object of our invention is to provide a new chemical product orcompound that is particularly adapted for use as a demulsifier in theresolution of crude oil emulsions.

Another object 01 our invention is to provide a practicable method formanufacturing said new chemical product or compound.

Although one of the primary objects of our invention is to provide a newcompound or composition of matter, that is-an emcient demulsifler forcrude oil emulsions of the water-in-oil type, the said compound orcomposition of matter is adapted for use in other arts, as hereinafterindicated. It also may have additional uses in various other fieldswhich have not yet been investigated.

We'have discovered that if one oxyalkylates glycerol so as to introduceat least three oxyalkylene radicals for each hydroxyl group, and if theproduct so obtained is reacted with a polybasic carboxy acid having notover eight carbon atoms, and in such a manner as to yield a fractionalester, due to the presence of at least one free carboxyl radical, onecan then esterify said acidic material or intermediate product with atleast one mole of an alcoholic compound of the type herein described togive a variety of new compositions of matter which have utility invarious arts, and particularly in the demulsification of crude oil.

The compounds herein contemplated may be product, which, in turn, isreacted with an alcoholic body of the kind hereinafter described, andmomentarily indicated by the formula R1(OH)11|.

Generically, the alcoholic body herein contemplated may be considered amember of the class in which 111. may vary from 1 to 10, although thespecific significance of m in the presentinstance will be hereinafterindicated. The second procedure is to react an alcohol of the formulatype Rl(OH)m with a polybasic acid, so as to produce an intermediateproduct, and then react said intermediate product or fractional esterwith the selected oxyalkylated glycerol.

Glycerol may be conveniently indicated by the following formula:

0H cat on If treated with an oxyallnvlating agent, and momentarilyconsideration will be limited to an oxyethylating agent, one may obtainan oxyethylated glycerol of the following formula:

in which the value of u may vary from 3 to 10 and all the values of nneed not be identical. If a polybasic carboxy acid be indicated by theformula:

coon

a-coon coon then the acyclic reaction product of one mole ofoxyethylated zlycerol and one mole of a polybasic car-boxy acid may beindicated by the following tormula:

I cimon-ooon ooom." C;H0:(C:H40)'H C|H|O)"H in which n" has the value ofl or 2. Similarly, if 2 moles of the polybasio acid be used, then thecompound may be indicated by the following formula:

ClH4O)n'OOCR-(COOH)1\" CIHI r-(CrHACD- OOCR(COOH).-

clmoh'n Likewise, if 3-moles of a polybasic acid are employed, thecompound may be indicated by the following formula:

clnlo 'oocmcoomw CrH|r-(CsH40).'OOCR(COOH).."

cnnowooomcoomw [(canoh-ooo inwhichzis0,1or2,1lis0, 1 or2,andzis 1,2or3,andz'is0or1,andu'is1or2.

It has been previously stated that compounds of the type hereincontemplated may be obtained by oxyalkylating agents, without beinglimited to ethylene oxide. Suitable oxyalkylating agents includeethylene oxide, propylene oxide, butylene oxlde and gLvcid, which,although not included, strictly speaking, by the unitary structureCIHIIO, is included within the meaning of the hereto appended claims andmay be simply considered as a variant of propylene oxide, 1.e.,-hydromropylene .oxide. Similarly, where a carbor vlic hydrogen atomappears, it may be replaced by metal, an ammonium radical, orsubstituted ammonium radical, or by an organic group derived from analcohol, such as an aliphatic alcohol, an aralkyl alcohol, or analicyclic alcohol. It may also be converted into an amide, including apolyaminoamide. Thus, the preceding formula may be rewritten in itsbroader scope, as follows:

in which n replaces the numbers 2, 3 or 4, Z includes the acidichydrogen atom itself. In the above formula, and hereafter, forconvenience, R1 is intended to include any hydroxyl groups that remain.

If the compounds herein contemplated are obtained under usualconditions, at the lowest temperatures, then the monomeric form is mostlikely to result. The production of the compounds herein contemplated isthe result of one or more esteriflcation steps. As is well known,esteriflcation procedures can be carried out in various manners, butgenerally speaking, esteriflcations can be carried out at the lowestfeasible temperatures by using one or several procedures. One procedureis to pass an inert, dried gas through the mass to be esterifled, andhave present at the same time a small amount of a catalyst, such asdried 1101 gas, a dried sulfonic acid, or the like. Another and betterprocedure, in many instances, is to employ the vapors of a suitableliquid, so as to remove any water formed and condense both the vapors ofthe liquid employed and the water in such a manner as to trap out thewater and return the liquid to the reacting vessel. This procedure iscommonly employed in the arts, and for convenience, reference is made toU. S. Patent No. 2,264,759, dated December 2, 1941, to Paul C. Jones.

Referring again to the last two formulae indicating the compounds underconsideration, it

I, can be readily understood that such compounds,

in numerous instances, have the property of polyfunctionality. In viewof this fact,'wh'ere there is at least one residual carboxyl and atleast one residual hydroxyl, one would expect that under suitableconditions, instead of obtaining the monomeric compounds indicated, onewould, in reality, obtain a polymer in the sense, for example, thatpolyethylene glycols represent a polymer of ethylene glycol. The term"polymer is frequently used to indicate the polymerized product derivedfrom a monomer in which the polymer has the same identical compositionas the monomer. In the present instance, however, polymerizationinvolves the splitting and loss of water so that the process isessentially self-esterification. Thus, strictly speaking, the polymericcompounds are not absolutely isomers of the monomeric compounds, butsince, for all practical purposes, they can be so indicated, and sincesuch practiceis common in the arts concerned'with materials of thistype, it is so adopted here. Thus, reference in the appended claims topolymers is intended to include the self-esteriflcation products of themonomeric compounds.

In view of what has been said, and in view of the recognized hydrophileproperties of the re curring oxyalkylene linkages, particularly theoxyethylene linkage, it is apparent that the materials hereincontemplated may vary from compounds which are clearlywater-solublethrough self-emulsifying oils, to materials which are balsam-like andsub-resinous or semi-resinous in nature. The compounds may vary frommonomers to polymers, in which the unitarystructure appears a number oftimes, for instance, 10 or 12 times. It is to be noted that true resins,i. e., truly not herein included. In other words, the polymerizedcompounds are soluble to a fairly definite extent, for instance, atleast 5% in some solvents, such 'as water, alcohol, benzene,dichloro-ethyl ether, acetone, oresylic acid, acetic acid, ethylacetate, dioxane or the like. This i simply another way of stating thatthe polymerized product contemplated must be of the sub-resinous type,which is commonly referred. to as an A resin, or a B resin, asdistinguished from a C resin, which is highly infusible, insoluble resin(see Ellis, Chemistry of Synthetic Resins (1935) me: 862, et seq.)

Reviewing the form as presented, it is obvious that one may obtaincompounds within the scope disclosed, which contain neither a freehydroxyl nor a free carboxyl group, and one may also obtain a compoundof the type in which there is present at least one free carboxyl, or atleast, one free hydroxyl, or both. The word polar" has sometimes beenused in the arts in this particular sense to indicate the presence of atleast one free hydroxyl group, or at least, one free carboxyl group, orboth. In the case of the free carboxyl group, the carboxylic hydrogenatom may, of course, be replaced by any ionizable hydrogen atomequivalent, such, for example, as a metal,

an ammonium radical, a substituted ammonium radical, etc. In the heretoappended claims the word "polar" is used in this specific sense.

insoluble materials of a hard plastic nature, are

ethylene diamine, etc.

We are aware that compounds similar to those contemplated in the presentinstance may be derived i'rom polyhydroxylated compounds having morethan three hydroxyl groups. For instance, they may be derived fromacyclic diglycerol, triglycerol, tetraglycerol, mixed polyglycerols,mannitol, sorbitol, various hexatols, dulcitol, pentaerythritol,sorbitan, mannitan, dipentaerythritol monoether, and other similarcompounds. Such particular types in which higher hydroxylated materialsare subjected to oxyalkylation and then employed in the same manner as"oxyalkylated glycerol is employed in the present instance, are notcontemplated in this specific case, although attention is directed tothes'ame.

Reference is also made to other oxyalkylated compounds which may be usedas reactants to replace oxyalkylated glycerol, or oxyalkylated ethyleneglycol, which latter reactant is described in a co-pending applicationhereinafter referred to. The reactants thus contemplated include thetype in which there is an amino or amido nitrorials, including thosehaving two or three hydroxyl groups, as well as those having more thanthree hydroxyl groups. For instance, theoxyalkylated derivatives,particularly the oxyethylated derivatives of ethyldiethanolamine,bis(hydroxyethyllacetamide, the acetamide oftris(hydroxymethyl-aminomethane, tetrahydroxylated Compounds may also bederived from cyclic diglycerol and the like.

Furthermore, for convenience, attention is directed to a somewhatsimilar class of materials which are described in our application SerialNo.

or the compounds hereinafter illustrated will refer to the use of maleicanhydride, although it is understood that any other suitable polybasicacid may be employed. Furthermore, reference is made to derivativesobtained by oxyethylation, although, as previously pointed out, otheroxyalkylating agents may be employed.

As far as the range of oxyethylated glycerols employed as reactants isconcerned, it is our preference to employ those in which approximately15 to 24 oxyethylene groups have been introduced into a single glycerolmolecule. This means that approximately five to eight oxyethyleneradicals have been introduced for each original hydroxyl group.

The oxyalkylation of glycerol is a well known procedure (see Example 11of German Patent No. 605,973, dated November 22, 1934, to I. G.Farbenindu'strie, A. G.). The procedure indicated in the following threeexamples is substantially identical with that outlined in saidaforementioned German patent.

Oxxnrmrmran GLYceaor.

. r Example 1 P 184 pounds oi. glycerol is mixed with 56%. by

weight, of caustic soda solution having a specific 384,595, filed March21, 1941, now U. .8. Patent No. 2,295,164, dated September 8, 1942. Saidpatent involves the use of the same ty of alcoholic bodies forreactants,'but is limited, among other things, to the compounds whichare essentially symmetrical in nature, for instance, involving theintroduction of two alcoholic residues, whereas, in the presentinstance, one, two, or three, or more, might be introduced.

As indicated previously, the polybasic acids employed are limited to thetype having not more than eight carbon atoms, for example, oxalic,malonic, succinic, glutaric, adipic, maleic, and phthalic. Similarly,one may employ acids such as fumaric, glutaconic, and various others,such as citric, malic, tartaric, andthe like. The selection of theparticular tribasic or dibasic acid employed, is usually concernedlargely with the convenience of manufacture of the finished ester, andalso the price or the reactions. Generally speakin phthalic acid oranhydride tends-to produce resinous materials, and greater care must beemployed if the ultimate or final product be of a sub-resinous type.Specifically, the preferred type of polybasic acid is such as tocongravity of 1.383. The caustic soda acts as a catalyst. The ethyleneoxide is added in relatively small amounts, for instance, about 44pounds at a time. The temperature employed is from 150- 180 C. Generallyspeaking, the gauge pressure during the operation approximates 200pounds at the maximum, and when reaction is complete, drops to zero, dueto complete absorption oi the ethylene oxide. When all of the ethyleneoxide has been absorbed and the reactants cooled, 'a

second small portion, for instance, 44 more pounds of ethylene oxide,are added and the procedure repeated until the desired ratio of 15 poundmoles of ethylene oxide to one pound mole of tain six carbon atoms orless. Generally speak- 1 desirable to use an acid which is moreresistant to pyrolysis. Similarly, when a polybasic acid is available inthe form ofan anhydride, such anhydride is apt to produce the ester withgreater ease than the acid itself. For this reason, maleic anhydrlde isparticularly adaptable, and also,

glycerol is obtained. This represents 660 pounds 'of ethylene oxide for92 pounds of glycerol.

Oxrarmaren Gtrceaor.

Example 2 The ratio of ethylene oxide is increased to 18 pound moles foreach pound mole 'of glycerol. Otherwise, the same procedure is followedas in Example 1, preceding.

Oxramnsrnn Gtxcrmor.

Example 3 'fhe same procedure is followed as in the two previousexamples, except that the ratio of ethylene oxide to glycerol isincreased to 21 to l.

I OXYETHYLATED GLYCEROL MALEATE Example 1 ceding example. except thattwo pound moles of maleic anhydride are employed so as to obtain thedimaleate instead of the monomaleate.

OxYs'rnYLA'rsn GLYCEROL MALEATI Example 3 The same procedure is followedas in th two preceding examples, except that three pound moles of maleicanhydride are employed so as to obtain the trimaleate.

OxYs'rHYLA'rmn GLYCEROL Marmara Example 4 The same procedure is employedas in the preceding examples, except that oxyethylated 81ycerol (ratio 1to 18) is substituted in place of oxyethylated glycerol (ratio 1 to 15)Oxxsnrruun GLYcsxor. Mama's: Example 5 The same procedure is employed asin the preceding examples, except that oxyethylated glycerol (ratio 1 to21) is employed instead of oxyethylated glycerol (ratio 1 to 15) or (1to 18).

Previous reference has been made to an alcoholic body which has beendefined generically by the formula R1(OH) 1n. The sub-generic class ofalcoholic compounds employed as reactants in the manufacture of thepresent compounds, are materials commonly referred to as high molalalcohol acids, or high molalhydroxy acids. They are invariablywater-insoluble. The commonest example is ricinoleic acid. Other hydroxyfatty acids include hydroxystearic acid, dihydroxystearic acid,diricinoleic acid, aleuritic acid, and the like. Similar acids areobtained in the oxidation of paraflin, petroleum hydrocarbon, or wax,and are commonly referred to as hydroxylated wax acids. fiydroxyiatedwax acids occur as by-products in the oxidation of waxes or similarmaterials, and are usually separated so that the commonest commercialform of oxidized wax acids represent mixtures comparative- 1y free fromthe hydroxylated compounds. Hydroxylated acids are produced by otherprocedures, such as chlorination, either by addition or substitution,as, for example, chlorination of oleic acid or stearic acid. Subsequentreactions involve the removal of the chlorine with the introduction of ahydroxyl radical. Undecylenic acid, derived from castor oil, has beenconverted into a hydroxy undecenoic acid. Unsaturated hydroxy acids,such as ricinoleic acid, may be treated in various manners, so as toproduce derivatives, for example, chlorinated or brominated ricinoleicacid. Such materials are entirely sat isfactory for use as reactants inthe preparation of materials of the kind herein contemplated.Naturally-occurring naphthenic acids can also be converted intohydroxylatcd products by following similar procedure. An unsaturatedhydroxy acid, such as ricinoleic acid, can be converted into ahydroxylated arylstearic acid. Such procedurecontemplates reactions suchas those invclving ricinoleicacid, benzene, and aluminum chloride inlarge excess, or-involvesthe desulfonation of a sulfo-aromatic fattyacid. In any event, by employing derivatives of undecylenic acid, or oneor more of the various wax acids, naturally-occurring naphthenic acid,ricinoleic acid, diriciholeic acid, or derivatives thereof, as have beenenumerated, one can obtain a variety of hydroxylated monocarboxy acids,having at least 11 carbon-atoms and not in excess of 36 carbon atoms.Such compounds are the kind herein contemplated as reactants to furnishthe alcoholiform hydroxyl.

Hydroxy acids of the kind herein contemplated may also be prepared bythe hydrolysis of alphahalogen acids. For instance, alpha-bromocaproicacid, alpha-bromocaprylic acid, alpha-bromocapric acid,alpha-bromolauric acid, alpha-bromomyristic acid, alpha-bromopalmiticacid, and the like, can be hydrolyzed to give the correspondingalpha-hydroxy acid. Indeed,'a reactive alpha-halogen acid may serve as afunctional equivalent of an alpha-hydroxy acid by liberation ofhydrochloric acid, instead of water. Such type of reaction, however,involves numerous dimculties;' and thus, it is better to employ ahydroiw acid.

In some instances, derivatives of hydroiwlated unsaturated acids aremost readily obtained by the employment of an intermediate in which thehydroxy group is protected. Thus, ricinoleic acid may be acetylated, andsuch acetyl ricinoleic acid converted into a derivative, for instance, aderivative in which an aryl group is introduced. Such derivative canthen be saponifled or hydrolyzed so as to regenerate the hydroxylradical.

-COMPLE'1ED Monoirsluc DERIVATIVE Example 1 One pound mole of av productof the kind described under the heading Oxyethylated glycerol maleate,Example 1" is reacted with one pound mole-of riclnoleic acid, preferablyin the absence of any high boiling hydrocarbon or inert solvent.

However, if an inert vaporizing solvent is employed, it is generallynecessary to use one which has a higher boiling range than xylene, andsometimes removal of such solvent might present a difllculty. Inother,instances, however, such high boiling inert vaporizing solvent, ifemployed,

- might be permitted to remain in the reacted mass and appear as aconstituent or ingredient of the final product. In any event, ourpreference is to conduct the reaction in the absence of any such solventand permit the reaction to proceed with the elimination of water. Thetemperature of reaction is about to 200 C. and time of reaction about 20hours.

COMPLETED MONOMERIC DsnrvA'rrvs:

Example 2 The same procedure is followed as in Completed monomericderivative, Example 1, preceding, except that the dimaleate describedunder the heading Oxyethylated glycerol maleate, Example 2" is usedinstead of the monomaleate.

COMPLETED MONOMIIRIC Dsarvll'rrvz Example 3 The same procedure isfollowed as in the two preceding examples, except that the trimaleate issubstituted for the monomaleate or dimaleate in the two precedingexamples.

COMPLETED Morrousnrc Drrsrva'rrvl:

Example 4 one pound mole of ricinoleic acid as a reactant, one employstwo pound moles.

COMPLETED MONOMERIC DERIVATIVE Example The same procedure is followed asin Example 3, preceding, except that for each pound mole of trimaleate,instead of adding-one pound mole of ricinoleic acid, one adds threepound moles of ricinoleic acid for reaction.

COMPLETED MONOMERIC DERIVATIVE Example 6 Reference to the precedingexamples will show that in each and every instance oxyethylated glycerol(ratio 1 to 15) has been employed as a raw material or primary reactant.In the present instance, a more highly oxyethylated glycerol isemployed, to wit, one involving the ratio of 1 to 18. (See Oxyethylatedglycerol maleate, Example 4, preceding.)

COMPLETED MONOMERIC DERIVATIVE Example 7 The same procedure is followedas in Exam-'- ple 6, immediately preceding, except that the oxyethylatedglycerol employed represents one having an even higher degree ofoxyethylation. For example, one indicated by the ratio of 1 to 21. (SeeOxyethylated glycerol maleate, Example 5, preceding.)

The method'of producing such fractional esters is well-known. Thegeneral procedure is to employ a. temperature above the boiling point ofwater anad below the pyrolytic point of the reactants. The products aremixed and stirred constantly during the heating and esteriflcation step.If desired, an inert gas, such as dried nitrogen or dried carbondioxide, may be passed through the mixture. Sometimes it is desirable toadd an esterification catalyst, such as sulfuric acid, benzene sulfonicacid, or the like. This is the same general procedure as employed in themanufacture of ethylene glycol dihydrogen diphthalate. (See U. S. PatentNo. 2,075,107, dated March 30, 1937, to Frasier.)

Sometimes esterification is conducted most readily in the presence of aninert solvent, that carries away the water of esterification which maybe formed, although as is readily appreciated, such water ofesterification is absent when such type of reaction involves an acidcol. However, if water is formed, for instance,

or intentional product. This is true in the present instance. ,In manycases when the compound is manufactured for purposes of demulsi- Vflcation, one is better off to obtain a polymer in the sense previouslydescribed, particularly a polymer whose molecular weight is a rathersmall multiple of the molecular weight of the monomer. For instance, apolymer whose molecular weight is two, three, four, five, or six timesthe molecular weight of the monomer. Polymerization is hastened by thepresence of an alkali, and thus in instances where it is necessary tohave a maximum yield of the monomer, it may be necessary to takeprecaution that the alkali used in promoting oxyethylation of glycerol,be removed before subsequent reaction. This, of course, can be done inany simple manner by conversion to sodium chloride, sodium sulfate, orany suitable procedure.

Previous reference has been made to the fact that the carboxylichydrogen atom might be variously replaced, by substituents, includingorganic radicals, for instance, the radicals obtained from alcohols,hydroxylated amines, nonhydroxylated amines, polyhydric alcohols, etc.Obviously, the reverse is also true, in that a free hydroxyl group maybe esterifled with a selected acid, varying from such materials asricinoleic acid to oleic acid, including alcohol acids, such ashydroxyacetic acid, lactic acid, ricinoleic acid and also polyba icacids of the kind herein contemplated.

With the above facts in mind, it becomes obvious that what has beenpreviously said as to polymerization, with the suggestion thatbyproducts or cogeneric materials were formed, may be recapitulated withgreater definiteness, and one can readily appreciate that the formationof heat-rearranged derivatives or compounds must take place to a greateror lesser degree. Thus, the products herein contemplated may becharacterized by being monomers of the type previously described, oresteriflcation polymers, or heat-rearranged derivatives of the same, andthus including the heat-rearranged derivatives of .both the polymers andesteriflcation monom ers, separately and Jointly. Although the class ofmaterials specifically contemplated in this instance is a comparativelysmall and narrow I anhydride, such as maleic anhydride, and a glyasxylene may be present and employed to carry oil the water formed. Themixture of xylene vapors and water vapors can be condensed so that thewater is separated. The xylene is then returned to the reaction vesselfor further circulation. This is a conventional and well known procedureand requires no further elaboration.

In the previous monomeric examples there is a definite tendency, inspite of precautions, at least in a number of instances, to obtainpolymeric materials and certain cogeneric by-products. This is typical,of course, of organic reactions of this kind,and as is well known,organic reactions per se are characterized by the fact that 100% yieldsare the exception, rather than the rule, and that significant yields aresatisfactory, especially in those instances where the by-products orcogeners may satisfactorily serve with the same purpose as the principalclass of a broad genus, yet it is obviously im possible to present anyadequate formula which would contemplate the present series in theircomplete ramification, except in a manner em played in the heretoappended claims.

Although the products herein contemplated vary so broadly in theircharacteristics, i. e., mom omers through sub-resinous polymers, solubleproducts, water-emulsifiable oils or compounds, hydrotropic materials,balsams, sub-resinous materials, semi-resinous materials, and the like,yet there is always present the characteristic unitary hydrophilestructure related back to the oxyalkylation. particularly theoxyethylation oi the glycerol used as the raw material. When our newproduct is used as a demulsifier, in the resolution 01' oil 'fleldemulsions, the demuisifier may be added to the emulsion at the ratio of1 part in 10,000, one part in 20,000, 1 part in 30,000, or for thatmatter, one part in 40,000. In such ratios it well may be that one cannot differentiate between the solubility of a compound completelysoluble in water in any ratio, and a semi-resinous product apparentlyinsoluble in water in ratios by which ordinary insoluble materials arecharacterized. However, at such ratios the importance must reside ininterracial position and the ability to usurp, preempt, or replace theinterfacial position previously occupied perhaps by the emulsifyingcolloid. In any event, reviewed in this light, the obvious commonproperty running through the entire series, notwithstanding variation inmolecular size and physical make-up, is absolutely apparent. Suchstatement is an obvious over simplification of the rationale underlyingdemulsiflcation, and does not even consider theresistance of aninter-facial iilm to crumbling, displacement, being forced intosolution, altered wetability, and the like. As to amidiiicationpolymers, for instance, where Z is the polyamino amide radical. see whatis said subsequently.

Courrrrzn Pormiuc DnrvA-rrvrs Ixcmmrno Eur-Runners Coosms Example 1COMPLETED Porvmmrc Drnrva'rrvzs Incnmmc Han-Rasmussen Coozszns Example 2The same procedure is followed as in the preceding example, except thatpolymerization is continued, using either a somewhat longer reactiontime, or it may be, a somewhat higher temperature, or both, so as toobtain a material having a molecular weight of approximately three tofour times that o! the initial product.

Comma-ran Pommsluc Dmarvsrrvzs Ixcummc HlAT-RIARRANGED Coommas Example 3The same procedure is followed as in Examples 1 and 2, preceding, exceptthat one employs reactants derived from more highly oxyethylatedglycerol, or from oxyethylated ricinoleic acid instead of ricinoleicacid, or from as intermediate involving both such reactants as rawmaterials.

ColtrLnzp POLYMERIC Dnlvs'rrvzs Incummo HsAr-RzARsANczn Coozms Example 4The same procedure is followed as in Examples 1 to 3,- preceding,'except that one polymerizes a mixture instead of a single monomer, forinstance, a mixture of materials of the kind described in Completedmonomeric derivative, Ex-

Example 4, are mixed in molecular proportion and subjected topolymerization in the manner indicated in the previous examples.

It is understood, of course, that the polymerized product need not beobtainedas a result of a twostep procedure. In other words, one need notconvert the reactants into the monomer and then subsequently convert themonomer into the polymer. The reactants may be converted through themonomer to the polymer in one step. Indeed, the formation of the monomerand polymerization may take place simultaneously. This is especiallytrue if polymerization is conducted in the absence of a liquid such asxylene, as previously described, and if one uses a comparatively highertemperature, for instance, approximately 200 C.

, stone and brick as a wetting agent and spreader ample 3, and inCompleted monomeric derivative,

for polymerization. Thus, one pound mole of oxyethylated glycerolmaleateof the kind described, ratio 1 to 15 up to 1 to 21, is mixed with twomoles of ricinoleic acid and reacted for 20 hours, at approximately 200,until the mass is homogeneous. It is stirred constantly during reaction.Polyi'unctionality may reside in dehydra tion (etherization) of twohydroxyl groups attached to dissimilar molecules.

The fact that the polymerized and heat-rearranged products can be madein asingle step, illustrates a phenomenon which sometimes occurs eitherin such instances where alcoholic bodies of the kind herein illustratedare contemplated as Y reactants, or where somewhat kindred alcoholicbodies are employed. The reactants may be mixed mechanically to give ahomogeneous mixture, or if the reactants do not mix to give ahomogeneous mixture, then early in the reaction stage, there is formed,to a greater or lesser degree, sufllcient monomeric materials so that ahomogeneous system is present. Subsequently, as reaction continues, thesystem may become heterogeneous and exist in two distinct phases, onebeing possibly an oily body of moderate viscosity, and the other being aheavier material, which is sticky or sub resinous in nature. In manyinstances it will be found that the thinner liquid material is a monomerand the more viscous or resinous material is a polymer, as previouslydescribed. Such prodnot can be used for demulsiflcation by adding asolvent which will mutually dissolve the two materials, or else, byseparating the two heterogen try; as wetting agents and detergents inthe acid washing of fruit, in the acid washing of building in theapplicationoi' asphalt in road building and the like, as a constituentof soldering flux preparations; as a flotation reagent in the flotationseparation of various minerals; for flocculation and coagulation ofvarious aqueous suspensions containing negatively charged particulessuch as sewage, coal washing waste water, and various trade wastes andthe like; as germicides, insecticides, emulsifiers for cosmetics, sprayoils, water-repellent textile finish, etc. Theseuses are by no meansexhaustive.

However, the most important use of the products herein described is asdemulsiflers for waterin-oil emulsions, and more specifically, emulsionsof water or brine in crude petroleum.

We have found that the particular chemical compounds or reagents hereindescribed may also be used for other purposes, for instance, as a.

break inducer in doctor treatment of the kind intended to sweetengasoline. (See U. 8. Patent No. 2,157,223, dated May 9, 1939, toSutton.)

Chemical compounds of the kind herein described are also of value assurface tension depressants in the acidization of calcareous oilbearingstrata by means of strong mineral acid, such as hydrochloric acid.Similarly, some members are eiiective as surface tension depressants orwetting agents in the flooding of exhausted oil-bearing strata.

As to using compounds of the kind herein described as flooding agentsfor recovering oil from subterranean strata, reference is made to theprocedure described in detail in U. 8. Patent No. 2,226,119, December24, 1940, to De Groote and R1 is a water-insoluble hydroxy acid radicalhavass'mss in which R is the carboxyl-free radical of a polycarboxy acidhaving not over 8 carbon atoms; R1 is a water-insoluble hydroxy acidradical hav ing at least 11 carbon atoms and not more than 36 carbonatoms; Z is an acidic hydrogen atom equivalent including the acidichydrogen atom itself; it represents the numerals 2 to 4; n representsthe numerals 3 to 10; n" represents the numerals 1 to 2: :1: representsthe numerals 0 to 2; 11 represents the numerals 0 to 2; .2 representsthe 30 numerals 1 to 3; :r' represents the numerals 0 to 1; and 11'represents the numerals 1 to 2.

2. An ester, being a member of the class consisting of monomers,sub-resinous esteriflcation polymers, and cogeneric sub-resinousheat-rearranged derivatives thereof, and of the following formula:

in which R is a carboxyl-free radical of a dicarboxy acid having notover 6 carbon atoms;

in which R is a carboxyl-free radical of a dicarboxy acid having notover 6 carbon atoms; R1 is a water-insoluble hydroxy acid radical havingat least 11 carbon atoms and not more than 36 carbon atoms; Z is anacidic hydrogen atom equivalent including the acidic hydrogen atomitself; 11. represents the numerals 3 to 10; :1: represents thenumerals-0 to 2; 11 represents the numerals 0 to 2; and 2 represents thenumerals 1 to 3.

4. An ester, being a polar member of the class consisting of monomers,sub-resinous esterification polymers, and cogeneric sub-resinousheatrearranged derivatives thereof, and of the follow- 1X18 formula:

[(CiHiOhC'O 0 CRC 0 OZ]: CIYHIOF-KCIEUOLVHII [(mmowooo aco 0R1]- inwhich R is a carboxyl-free radical of a dicarboxy acid having not over 6carbon atoms; R1 is a water-insoluble hydroxy acid radical having atleast 11 carbon atoms and not more than 36 carbon atoms; Z is an acidichydrogen atom equivalent including the acidic hydrogen atom itself; nrepresents the numerals 3 to 10 :1: represents the numerals 0 to 2; 1!represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

5. An ester, being a polar acidic member of the class consisting ofmonomers, sub-resinous esterification polymers, and cogenericsub-resinous heat-rearranged derivatives thereof, and of the followingformula:

in which R isa carpoxyl-free radical of a dicarboxy acid having not over6 carbon atoms; R- is a water-insoluble hydrcxy acid radical having atleast 11 carbon atoms and not more than 36 carbon atoms; Z is an acidichydrogen atom equivalentincluding the acidic hydrogen atom itself; nrepresents the numerals 3 to 10; .1: represents the numerals 0 to 2: 11represents the numerals 0 to 2; and 2 represents the numerals 1 to 3.

6. An ester, being a polar acidicmember of the class consisting ofmonomers, sub-resinous asterificationi polymers; and cogenericsub-resinous heat-rearranged derivatives thereof, and of the followingformula:

in which R is a carboxyl-free radical of a dicarboxy acid having notover 6 carbon atoms; R1 is a water-insoluble hydroxy acid radical havingat least 11 and not more than 18 carbon atoms; 2 is an acidic hydrogenatom equivalent including the acidic hydrogen atom itself; n representsthe numerals 3 to 10; a: represents the numerals 0 to 2;11 representsthe numerals 0 to 2; and .2 represents the numerals 1 to 3.

7. An ester, being a polar acidic member of the class consisting ofmonomers, sub-resinous esterification polymers, and cogenericsub-resinous heat-rearranged derivatives thereof, and of the followingformula:

in which R is a carboxyl-free radical of a dicarboxy acid having notover 6 carbon atoms;

R1 is a water-insoluble hydroxy fatty acid radical having at least 11and not more than 18 carbon atoms; Z is an acidic hydrogen atomequivalent including the acidic hydrogen atom itself; 11'

represents the numerals 3 to 10; 1: represents the numerals 0 to 2; 1represents the numerals 0 to 2;'

and 2 represents the numerals 1 to 3.

8. An ester, being a polar acidic member of the class consisting ofmonomers, sub-resinous esterification polymers, and cogenericsub-resinous heat-rearranged derivatives thereof, and of the followingformula:

[(C:H|O).IO0CRCO0Z].

in which R is a carboxyl-free radical of a dicarboxy acid having notover 6 carbon atoms; R1 is a riclnoleic acid radical; Z is an acidichydrogen atom equivalent including the acidic hydrogen atom itself; 11'represents the numerals 3 to 10; :1: represents the numerals 0 to 2; 11

